AU635061B2 - Bitumen compositions - Google Patents

Abstract

The invention provides bitumen compositions comprising bitumen and at least one polymerised fatty acid contained in the bitumen, processes for their preparation and their use in bitumen emulsions and surface dressings suitable for roads.

Description

635061 S F Ref: 137473 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: Class Int Class Complete Specification Lodged: Accepted: Published: Priority: Related Art: 0 1.

I

Name and Address of Applicant: Address for Service: Shell Internationale Research Maatschappij B.V.

Carel van Bylandtlaan 2596 HR The Hague THE NETHERLANDS Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia 0 0 Complete Specification for the invention entitled: Bitumen Compositions The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/3 I T 5954 FF

ABSTRACT

BITUMEN COMPOSITIONS The invention provides bitumen compositions o* comprising bitumen and at least one polymerised fatty acid contained in the bitumen, processes for their preparation and their use in bitumen emulsions and S surface dressings suitable for roads.

S.

*4 o eg oOOO PS17014

IA

T 5954 FF BITUMEN COMPOSITIONS This invention relates to bitumen compositions, their preparation, and their use in bitumen emulsions and surface dressings, e.g. for road surfacing.

e Venezuelan crude oils naturally contain naphthenic acids. Bitumens prepared from such crude oils (naphthenic bitumens) contain the napththenic S acids and have improved properties relative to bitumens (non-napthenic bitumens) prepared from crude oils which do not contain naphthenic acids, e.g.

0 Middle East oils. It is known to add (and incorporate) naphthenic acids to non-naphthenic bitumens in order to try to attain the quality of a naphthenic bitumens.

Australian Patent No. 557974 (Kao Corp.) discloses a liquid emulsifier composition suitable for preparing an asphalt (bitumen) emulsion which is dispersible in cold water and which comprises at least one mono- or poly-amine containing a C 8 22 aliphatic group, and at least one carboxylic acid that is C20 straight-chain saturated, C 4 18 branched chain saturated, C 12 -18 straight-chain unsaturated, C 5 18 saturated, containing a naph-ienic ring, C 7 18 aromatic, containing a PS17014 2 benzene ring, or a dimer acid, mainly a C 3 6 dicarboxylic acid.

It has now surprisingly been found that bitumen compositions having surprisingly enhanced properties can be obtained by incorporating polymerised fatty acids into bitumens.

According to the present invention therefore there is provided a bitumen composition comprising bitumen and at least one polymerised fatty acid contained (incorporated) in the bitumen.

Polymerised fatty acids, particularly dimer and trimer acids, typically contain alkyl chains greater S. than 4 carbon atoms, preferably at least 7 carbon atoms, and may be obtained by polymerisation of 15 unsaturated fatty acids such as tall oil fatty acids and linoleic acid, Dimer acids (fatty acids, C -unsaturated dimers) are known and are assigned 18 Chemistry Abstracts Registry Number CAS/61788-89-4.

Trimer acids (fatty acids, C 8-unsaturated trimers) '0 are also known (CAS/68937-90-6). Such polymerised fatty acids are described, for example, in Kirk-Othmer, Encyclopedia of Chemical Technology, Vol, 7, pages 768 to 782, 3rd Ed. (1979), John Wiley Sons Inc., USA, and examples are commercially 25 available, e.g. under the trade mark "PRIPOL" (Unichema International, and the trade mark "POLYMERGIN" (Harburger Fettchemie Brinckman Mergell W. Germany). They can also be prepared by plasma polymerisation, e.g. by the method described in EP-A-346 999.

Preferably, the at least one polymerised fatty acid comprises at least one acid selected from dimers and trimers of an unsaturated fatty acid, advantageously at least one acid selected from dimers and trimers of a C 18 unsaturated fatty acid. A PS17014 3 particularly preferred polymerised fatty acid mixture comprises a blend containing 4 parts by weight C 36 dimer acid to 1 part by weight trimer acid, e.g. the dimer acid sold under the trade mark "PRIPOL 1017".

The proportions of the at least one polymerised fatty acid relative to the bitumen are not critical.

However the at least one polymerised fatty acid is preferably present in an amount of at least 0.1% w/w of the bitumen, e.g. an amount in the range 0.1% to 2% w/w of the bitumen, more preferably at least w/w of the bitumen, e.g. an amount in the range to 1% w/w of the bitumen.

The invention also provides a process for preparing a bitumen composition of the invention S 5 which process comprises incorporating the at least one polymerised fatty acid into the bitumen, conveniently by mixing the acid component directly into molten bitumen. The bitumen may be any bitumen, but the advantages of the invention are most clearly attained when the bitumen is a non-naphthenic bitumen, as will readily be appreciated by those skilled in the art.

Emulsions and surface dressings, e.g. for road surfacing may readily be prepared from bitumen 25 compositions of the invention, in known manner.

The invention thus further includes the use of bitumen compositions according to the invention in a bitumen emulsion or a surface dressing suitable for roads.

The invention will be further understood from the following illustrative examples, in which parts and percentages are by weight unless otherwise indicated.

PS17014 4

EXAMPLES

Various doped bitumens were prepared based on five 180/220 penetration bitumens, viz. an industrially produced bitumen (Bitumen A) and S laboratory bitumens prepared by blending well defined short residues from crude oils of different geographical origins with wash oils from the same crude oils, i.e. Aral Heavy (Bitumen Maya Isthmus (Bitumen Ural (Bitumen or by including a vacuum flashed thermally cracked residue (Ural) (Bitumen E).

.The bitumens were doped by adding doping agents to the molten bitumens whilst stirring until homogeneous.

Emulsions containing about 65% bitumen were prepared in conventional manner from the above bitumens, by introducing bitumen (at 140°C) into a turbine mill together with an aqueous phase containing hydrochloric acid and emulsifier ("DINORAM S" cationic emulsifier ex CECA, France. (DNS)).

Various properties of the bitumens (adhesivity) e'o. and of the emulsions viscosity, breaking 4* behaviour) were measured, and the results are given in Tables 1 to 6 following, in which the doping agent RCO (also known as NOR 90) is a naphthenic acid used for purposes of comparison, "PRIPOL 1013" and "PRIPOL 1017" are dimer acids (Unichema International, UK), "PRIPOL 1049" is a trimer acid (Unichema International, UK), "POLYMERGIN D75" is a mixture of -0 polymerised fatty acids with a high trimer acid content (Harburger Fettchemie Brinckman Mergell GmbH), and "P4" is a mixture obtained by plasma polymerisation by the method of EP-A-346 999 containing approximately 20% of dimer and 40% of PS17014 trimer acids. Various properties of these dixner and trimer acids are given in Table A immediately following: 9.* 0* 9. 0 9 6*ee 0 9 9* 0

S

SO

0* 0 55 S S *0 a.

0

SOS

9 050909 0 PS17014 *.e 4 S 4 S S 4, C SO 4 5* S C S S S *5 5 *5 S *5 S S S* S 9 4 a C S S *4 5 5 4 5.5 5

C

S

S. 5 9 *9 -6 TABLE A DIMER/TRIMER ACID VALUE VISCOSITY MONOMER DINER TRIMER ACID AT 25*C ACID ACID ACID (mg KOH/g) (Pa.s) (36) "PRIPOL 1013 196 7.1 Trace 95 "PRIPOL 1017"1 194 8.2 2 79 19 "PRIPOL 1049"1 189 40.0 Trace 4 96 "POLYMERGIN D7511 185 8 5 75 P4 (plasma) 182 solid 45 20 PS 17 014 -7 TABLE 2.

BITUMEN 180/220 A A A A DOPE RCO RCO 0% 0 2 2 Penetration 15*C Penetration 25*C Acid Number 53 193 0 Adhesivity Quartz ite Flint Limestone Diorite it b i.

a a 4' 4q* 9

S

4 5 a a.

S 25 0 25 75 1.5 1.0 2.5 53 193 0 25 0 25 75 1.5 1.0 2.6 190 2 0 AQUEOUS PHASE DNS kg/t HC1 kg/t pH 1.5 1.0 2.6 2.6 a a 9.54 as 4* 5

S.

S a.

tie

S

'SaSS,

S

EMULS ION~ Bitumen content %65.2 pH 3.1 Pseudo-viscosity Engler 20*C (degrees) 12.2 STV 250C expressed in cSt. (mm 2/S) 92 Breaking Rate LCPC 100 SMS 210m 64 .9 3.2 9.7 65.1 3.0 64. 0 3.2 14.0 10.9 73 105 110 1.6 100 6.7 PS 17 014 8 TABLE 1 (continued) BITUMEN 180/220 A A A A Storage Stability decantation %1.2 1.6 1.1 1.1 sediment U 65.5 L74.7 9.2 5.9 6.3 13.3 sieve Residue 630 ALm <0.1 <0.1 <0.1 <0.1 160 m~ i <0.1 <0.1 <0.3.

B..63 m 0.4 0.3 0.4- *38 M 2.2 1.8 1.2 PS137 014 9- TABLE 2 BITUMEN 180/220 A A A A

"POLJY-

DOPE "PRIPOL "PRIPOL "PRIPOL MERGT.N 1013"1 1017" 1049" 0.5% 0.5% Penetration 15 *C Penetration Acid Number 1.2 1.2 4 *0 a.

Adhesivi% .y Q'nartz ite mt Limestone Diorite 100 AQUEOU6 PHASE DNS kg/t HC1 kg/t pH EMULS ION Bitumen content% pH Pseudo-viscosity Engler (degrees) STV expressed in cSt (mm 2/S 1.5 1.0 2.5 63.*7 3.0 10. 2 77 1.5 0.9 2.8 64 .7 3.0 12.9 97 1.5 0.9 2.8 64 .0 3.0 11. 0 2.6 65. 1 3.1 I,.8 *5* 0.

83 104 PS 17 014 10 TABLE 2 (continued) BITUMEN 180/220 A A A A

"POLY-

DOPE "PRIPOL "PRIPOL "PRIPOL MERGIN 1013"1 1017"1 1049"1 D;51 0.5% 0.5% 9* ~0 V 9~*e a a a ce..

Breaking Rate

LCPC

SMS 210m Storage Stability decantation% sediment U sieve Residue 630 A mn 38 Ai m 95 9.3 1.0 63 .3 70.3 7.0 1 1 1 0.4 85 10. 8 1. 1 64 .4 68 .5 4.1

I

1 0.2 0.6 70 7.3 1. 1 64 .2 69. 6 5.4 1 1 0.1 0.4 5.2 0.6 64.7 69. 6 4.9 1 1 1 0.31 a. a a a a a a.

a a a.

a.

a ,*a PS17O 1.4 11 TABLE 3 BITUMEN A A A A DOPE P4 P4 "PRIPOL "PRIPOL 1013" 1049" 1.0% 1.0%

WI

I

I. I I. I

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111111 I I 0 Penetration 15*C Penetration 25*C Acid Number Adhes iv ity Quartzite Flint Limestone Diorite AQUEOUS PHASE DNS kg/t HC1 kg/t pH EMULS ION Bitumen content% pH Pseudo-viscosity Engler (degrees) STV 25'C expressed in cSt (mm 2/s 55 214 2.1 1.9 1.5 1.0 2.6 53 203 2.2 1.5 1.0 2.6 1.5 1.0 2.6 1.c 2.6 911

I

I I I. I

I.

I I

I.

I

I..

111114 65.4 65.0 2.9 2.8 65. 0 2.7 34.7 43 568 65.0 2.6 20.2 19 251 13.4 18.6 16.1 213 PS17 014 12 TABLE 3 (continued) BITUMEN A A A A DOPE P4 P4 "PRIPOL "PRIPOL 1013" 1049" 1.0% 1.0% Breaking Rate LCPC 80 55 70 SMS 210mn 5.1 29 27.5 42.7 Storage Stability decantation 0.0 0.0 1 1) sedimnent U 59.6 65.6 64.7 65.1 L 70.5 67.7 66.8 67.6 A10.9 2.1 2.1 Sie~ve? Residue 630 mILI <0.1 <0.1 <0.1 <0.1 160 miI <0.1 <0.1 <0.1 <0.1 :.63 m~i 0.3 <0.1 <0.1 <0.1 38 mL i 1.2 0.4 0.2 <0.1 PS17 014 13 TABLE 4 BITUMEN 180/220 B B C C DOPE "PRIPOL "PRIPOL 1017" 10171) *9 9 9 9 9 9* 9 Penetration 15*C Penetration 25*C Acid Number Adhes ivity Quartz ite Flint Limestone Diorite AQUEOUS PHASE DNS kg/t HC1 kg/t pH

EMULSIOW

Bitumen content% 63 215 0 62 205 0 0 25 50 50 1.5 1.0 2.5 64.5 50 75 100 75 1.5 1.0 2.5 25 75 50 75 1.5 1.0 2.5 100 9S*4

I

9**9 *0 9* In ft. *,a 64.7 64.7 64.6 2.8 3.6 3.1 3.1 Pseudo-viscosity Engler 20'C (degrees) STV expressed in cSt (mm 2/s 10.9 14.1 20.1 317 82 106 151 PS 17 014 14 TABLE 4 (continued) BITUMEN 180/220 B B C C DOPE "PRIPOL "PRIPOL 1017" 1017"1

U@

V.

V

V

V

V S V

V

V.

9 Breaking Rate

LCPC

SMS 210mn Storage Stability decantation% sediment %U

%L

Sieve Residue 630 A. int 160 g~ m 63 ji m 38 A mn 105 1.4 80 100 7.0 1.6 0.9 7.7 <0 1 1 0.4 1.7 1.4 63.8 70. 5 6.7 1 1 0.1 0.4 1 1. 0.8 64.2 68.7 1 9.

V..

V

V

9* S

V.

V 9

V.

1 1 0.3 1.5 1 1 0.1

S

V..

W*VV*

PS 17014 15 TABLE BITUMEN 180/220 D D D DOPE RCO "PRIPOL 1017"1 t S.* a a a a. *a a 4**a Penetration 15'C Penetration 25*C Acid Number Adhes ivity Quartz ite Flint Limestone Diorite AQUEOUS PHASE DNS kg/t HC1 kg/t pH 25 50 25 50 1.5 1.0 2.5 100 62 213 0 1.5 1.0 2.5 S. a a a. *6 a a EMULS ION Bitumen content% pH Pseudo-viscosity Engler 20*C (degrees) STV expressed in cSt (mm 2

/S

64.5 64.1 64.4 3.5 3.2 3.1 a.

a .aa a a 14.0 18.1 11.4 105 136 PS17 014 16 TABLE BITUMEN 180/220 D D D DOPE RCO "PRIPOL 1017"1 Breaking Rate

LCPC

SMS 210m 105 1.8 90 4.05 8.2 00 0 Storage Stability decantation% sediment U 1.2 0.6 0.0 64 .9 68 .3 3.4 6.3 Sieve Residue 630 g m 160A. mn 63 p m 38 /1 In 0 boo 6 boo 1 1 0.2 1.4 1 1 0.1 1.3 1 1 1 1 PS 17 014 17 TABLE 6 BITUMEN 180/220 E E E DOPE RCO "PRIPOL 1017"1 S S 5. 9

S

S

S

*5 S S Penetration 15'C Penetration 25*C Acid Number Adhes ivity Quartz ite Flint Limestone Diorite AQUEOUS PHASE DNS kg/t HC1 kg/t pH 100 100 64 223 0 1.5 1.0 2.5 1.5 1.0 2.5 5 C S *0

OS

S

S..

S

EMULS ION Bitumen content pH Pseudo-viscosity Engler 20'C (degrees) STV expressed in cSt (mm 2/s) 64.7 64.3 65.0 3.3 3.3 13.2 14.1 99 106 9.7 PS170 14 18 TABLE 6 (continued) BITUMEN 180/220 DOPE RCO "PRIPOL 1017"1 Breaking Rate

LCPC

SMS 210mn 100 1.7? 80 8.1 17 .2 *0 as of S.6.

400 Storage Stability decantation% sediment U 1.6 1. 1 0.8 63. 0 70.9 7.9 9.9 8.2 Sieve Resi ~e 630 mti 160,u mn 63 m i 38 mIi 1 1 0.2 1.4 1 1 0.2 1.0 1 1 0.1 0.1

*S

S

9* S S PS17 014 19 The results of tests on the various emulsions given in Tables 1 to 6 above are illustrated in figures in the accompanying drawings, Figures 2 to being concerned with the effect of doping on break performance. In the figures constituting the accompanying drawings: Figure 1 shows the effect of doping dimer and trimer acids on the X axis) on the pseudoviscosity of the emulsion (expressed in cSt (mm for various acid mixtures; Figure 2 records the SMS 210m test on the X axis and the LCPC test (g/100g) on the Y axis for emulsions prepared from a bitumen A which is undoped or doped with different agents; e* 5 Figure 3 is similar to Figure 2, but relates to different Bitumens, either undoped or doped with the same agent ("PRIPOL 1017"); Figure 4 shows of dimer and trimer acids on the X axis and percentage deposited on the Y axis, as recorded in the SMS 210m test; to 00 Figure 5 shows percentages of dimer and trimer acids on the X axis and filler (g/ilGg) on the Y axis, as recorded in the LCPC test; and 25 Figure 6 shows the effect of "PRIPOL 1017" on the mean adhesiveness, pseudoviscosity and sedimentation of an emulsion, compared with an undoped bitumen.

In the above Tables 1 to 6 and Figures 1 to 6, pseudoviscosity was measured in known manner using an PS17014 20 Engler viscometer and using a standard tar viscometer (STV). The abbreviations under "Storage bility" refer to upper layer lower layer and the difference therebetween (Greek letter delta).

Adhesivity of the bitumen and breaking rates of the emulsions were tested as follows: 1. ADHESIVITY (LCPC method) The purpose of this test is to assess the adhesivity, in the presence of water, of a hydrocarbon binder coated on aggregate, and in it the displacement of bitumen by water on the surface of the aggregate is measured. In the test, bitumen-coated aggregate is plunged into 15 water while hot, and the percentage of the surface covered by the binder after 16 hours' immersion at 60*C is evaluated. The test is carried out with four types of reference aggregate, as indicated.

2. LCPC break index Reference fines (siliceous fines in the case of cationic emulsions) are poured continuously through a funnel at a rate of 0.3 to 0.5 g/s 25 into a beaker containing 100g of emulsion. The mixture is agitated constantly, and the addition of fines halted when the aggregate-emulsion system takes on the appearance of a block. The quantity of fines added to the 100g of bitumen emulsion is called the break index.

3. SMS 210m break index of aggregate (Corbigny porphyry, 2 to 4mm) are placed in contact with an excess of emulsion (about 10g) for 1 hour in an environment PS17014 21 saturated with water in order to prevent any evaporation. The unbroken emulsion is removed with distilled water. After drying, the quantity of bitumen deposited is determined by weighing, and the result expressed in relation to 10g of emulsion.

From the Tables and the Figures (particularly Figure 2) it is evident that all the dimer/trimer acids significantly improved the breaking performance of the emulsions.

Overall, the dimer acid "PRIPOL 1017" is the most preferred dimer/trimer acid for its combination of improvements in relation to adhesivity of the 15 bitumens and sedimentation performance (Figure 5) and breaking behaviour (Figure 6) of the emulsions.

0 PS17014

Claims (11)

1. A bitumen composition comprising bitumen and at least one polymerised fatty acid contained in the bitumen, produced by a process which comprises incorporating the at least one polymerised fatty acid into the bitumen by mixing the acid or acids directly into molten bitumen.

2. A composition according to Claim 1 wherein the at least one polymerised fatty acid comprises at least one acid selected from dimers and trimers of an unsaturated fatty acid.

3. A composition according to Claim 1 or 2 wherein the at least one polymerised fatty acid comprises at least one acid selected from dimers and trimers of a C 18 unsaturated fatty acid.

4. A composition according to any one of Claims 1 to 3 wherein the at least one polymerised fatty acid is present in an amount of at least 0.1% w/w of the bitumen.

5. A composition according to Claim 4 wherein the amount is at least 0.5% w/w of the bitumen.

6. A composition according to Claim 4 or 5 wherein the amount is up to 2% w/w of the bitumen.

7. A composition according to Claim 6 wherein the amount is in 20 the range 0.5% to 1% w/w of the bitumen.

8. A process for preparing a bitumen composition according to any one of claims 1 to 7 which comprises incorporating the at least one polymerised fatty acid into the bitumen by mixing the acid or acids directly into molten bitumen.

9. Use of a composition according to any one of Claims 1 to 7 in a bitumen emulsion or a surface dressing suitable for roads.

10. A bitumen composition comprising bitumen and at least one polymerised fatty acid contained in the bitumen substantially as hereinbefore described with reference to any one of the Examples. 30

11. The product of the process of Claim 8. DATED this TWENTY-FOURTH day of DECEMBER 1992 Shell Internationale Research Maatschappij B.V. -Patent Attorneys for the Applicant SPRUSON FERGUSON 0661T/jj